Probing into the In-Situ Exsolution Mechanism of Metal Nanoparticles from Doped Ceria Host.
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ABSTRACT:
SUBMITTER: Zhang L
PROVIDER: S-EPMC8398560 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:The reduction of pure and Sm-doped ceria in hydrogen has been studied by synchrotron-based in situ X-ray diffraction to eventually prove or disprove the presence of crystalline cerium hydride (CeH x ) phases and the succession of potential structural phase (trans)formations of reduced cerium oxide phases during heating-cooling cycles up to 1273 K. Despite a recent report on the existence of bulk and surface CeH x phases during reductive treatment of pure CeO2 in H2, structural analysis by Rietveld refinement as well as additional 1H-NMR spectroscopy did not reveal the presence of any crystalline CeH x phase. Rather, a sequence of phase transformations during the re-cooling process in H2 has been observed. In both samples, the reduced/defective fluorite lattice undergoes at first a transformation into a bixbyite-type lattice with a formal stoichiometry Ce0.58 3+Ce0.42 4+O1.71 and Sm0.15 3+Ce0.39 3+Ce0.46 4+O1.73, before a transformation into rhombohedral Ce7O12 takes place in pure CeO2. This phase is clearly absent for the Sm-doped material. Finally, a triclinic Ce11O20 phase appears for both materials, which can be recovered to room temperature, and on which a phase mixture of bixbyite Ce0.66 3+Ce0.34 4+O1.67, rh-Ce0.60 3+Ce0.40 4+O1.70 and tri-Ce0.48 3+Ce0.52 4+O1.76 (for pure CeO2) or bixbyite Sm0.15 3+Ce0.47 3+Ce0.38 4+O1.69 and tri-Sm0.15 3+Ce0.31 3+Ce0.54 4+O1.77 (for Sm-doped CeO2) prevails. The absence of the rhombohedral phase indicates that Sm doping leads to the stabilization of the bixbyite phase over the rhombohedral one at this particular oxygen vacancy concentration. It is worth noting that recent work proves that hydrogen is indeed incorporated within the structures during the heat treatments, but under the chosen experimental conditions it has apparently no effect on the salient structural principles during reduction.
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Project description:Exsolution, an innovative method for fabricating perovskite-based oxides decorated with metal nanoparticles, has garnered significant interest in the fields of catalyst fabrication and electrochemical devices. Although dopant exsolution from single perovskite structures has been extensively studied, the exsolution behaviour of double perovskite structures remains insufficiently understood. In this study, we synthesized B-site double perovskite Ru-doped lanthanum nickel titanates with a 7.5 at% A-site deficiency, and systematically investigated the exsolution process that formed nickel metal nanoparticles on the material surface, across a broad reduction temperature range of 350-1000 °C. Both Ex situ and in situ characterization revealed that small, uniform Ni nanoparticles exsolved at low temperatures, whereas the exsolution of ruthenium required higher reduction temperatures beyond 1000 °C. Within the reduction temperature range of 350-500 °C, a notable finding is the reconstruction of exsolved nanoparticles, implying that Ni particles exist in a thermodynamically metastable state. Electrochemical impedance spectroscopy (EIS) showed a decreased area specific resistance (ASR) during the progress of exsolution. The increase in current density of a full solid oxide cell (SOC) in electrolysis mode and the doubling of peak power density in fuel cell mode attributed to the exsolution of Ni nanoparticles highlight the potential application of metal exsolution in electrode materials for SOCs.
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